U.S. patent number 10,381,571 [Application Number 14/844,439] was granted by the patent office on 2019-08-13 for compound, organic light emitting element comprising same, and display device comprising organic light emitting element.
This patent grant is currently assigned to SAMSUNG SDI CO., LTD.. The grantee listed for this patent is SAMSUNG SDI CO., LTD.. Invention is credited to Mi-Young Chae, Jin-Seok Hong, Dal-Ho Huh, Yu-Na Jang, Young-Kyoung Jo, Sung-Hyun Jung, Jun-Seok Kim, Han-Ill Lee, Seung-Jae Lee, Dong-Kyu Ryu, Dong-Wan Ryu.
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United States Patent |
10,381,571 |
Ryu , et al. |
August 13, 2019 |
Compound, organic light emitting element comprising same, and
display device comprising organic light emitting element
Abstract
A compound, an organic light emitting element including the
same, and a display device including the organic light emitting
element are disclosed, and the compound for an organic optoelectric
device represented by Chemical Formula 1 is provided.
Inventors: |
Ryu; Dong-Wan (Suwon-si,
KR), Huh; Dal-Ho (Suwon-si, KR), Jung;
Sung-Hyun (Suwon-si, KR), Hong; Jin-Seok
(Suwon-si, KR), Kim; Jun-Seok (Suwon-si,
KR), Ryu; Dong-Kyu (Suwon-si, KR), Lee;
Seung-Jae (Suwon-si, KR), Lee; Han-Ill (Suwon-si,
KR), Jang; Yu-Na (Suwon-si, KR), Jo;
Young-Kyoung (Suwon-si, KR), Chae; Mi-Young
(Suwon-si, KR) |
Applicant: |
Name |
City |
State |
Country |
Type |
SAMSUNG SDI CO., LTD. |
Yongin-si, Gyeonggi-do |
N/A |
KR |
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Assignee: |
SAMSUNG SDI CO., LTD.
(Yongin-si, Gyeonggi-do, KR)
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Family
ID: |
51989034 |
Appl.
No.: |
14/844,439 |
Filed: |
September 3, 2015 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20150380659 A1 |
Dec 31, 2015 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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PCT/KR2013/007135 |
Aug 7, 2013 |
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Foreign Application Priority Data
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May 27, 2013 [KR] |
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10-2013-0059800 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L
51/006 (20130101); C09K 11/06 (20130101); C07D
417/12 (20130101); C07D 413/14 (20130101); C07D
409/14 (20130101); C07D 413/12 (20130101); C07D
409/12 (20130101); C07D 417/14 (20130101); H01L
51/0059 (20130101); C07D 333/76 (20130101); C07D
405/12 (20130101); H01L 51/052 (20130101); H01L
51/0071 (20130101); C07D 307/91 (20130101); H01L
51/0052 (20130101); H01L 51/0072 (20130101); H01L
51/0074 (20130101); C07D 405/14 (20130101); H01L
51/0061 (20130101); H01L 51/0073 (20130101); H01L
51/5092 (20130101); C09K 2211/1077 (20130101); H01L
51/5072 (20130101); H01L 51/5096 (20130101); C09K
2211/1081 (20130101); H01L 51/5088 (20130101); H01L
51/5056 (20130101); H01L 51/5012 (20130101) |
Current International
Class: |
H01L
51/54 (20060101); C07D 413/14 (20060101); C07D
405/12 (20060101); C07D 409/12 (20060101); C07D
409/14 (20060101); C07D 413/12 (20060101); C07D
417/12 (20060101); C07D 417/14 (20060101); C09K
11/06 (20060101); H01L 51/00 (20060101); C07D
333/76 (20060101); C07D 307/91 (20060101); H01L
51/05 (20060101); C07D 405/14 (20060101); H01L
51/50 (20060101) |
References Cited
[Referenced By]
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Oct 2012 |
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WO |
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Other References
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Pu et al. Organic Electronics 2010, 11, 479-485. Date of online
publication: Dec. 16, 2009. cited by examiner .
Chang Woo Seo, et al., "Thin Solid Films", 2012, vol. 520, pp.
7022-7025. cited by applicant .
Yong Joo Cho, et al., "Low Driving Voltage, H igh Quantum
Efficiency, High Power Efficiency, and Little Efficiency Roll-Off
in Red, Green, and Deep-Blue Phosphorescent Organic Light-Emitting
diodes Using a High-Triplet-Energy Hole Transport Material",
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applicant .
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Corresponding European Patent Application No. 13885531.7. cited by
applicant .
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|
Primary Examiner: Bohaty; Andrew K
Attorney, Agent or Firm: Lee & Morse, P.C.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of pending International
Application No. PCT/KR2013/007135, entitled "Compound, Organic
Light Emitting Element Comprising Same, and Display Device
Comprising Organic Light Emitting Element," which was filed on Aug.
7, 2013, the entire contents of which are hereby incorporated by
reference.
Claims
What is claimed is:
1. A compound represented by Chemical Formula 1: ##STR00172##
wherein, in Chemical Formula 1, L.sup.1 to L.sup.6 are each
independently a substituted or unsubstituted C6 to C30 arylene
group, or a substituted or unsubstituted C2 to C30 heteroarylene
group except a substituted or unsubstituted fluorenylene group, n1
to n6 are each independently integers ranging from 0 to 3, R.sup.1
to R.sup.6 are each independently hydrogen, deuterium, a
substituted or unsubstituted C1 to C30 alkyl group, a substituted
or unsubstituted C3 to C30 cycloalkyl group, a substituted or
unsubstituted C6 to C30 aryl group, a substituted or unsubstituted
C2 to C30 heteroaryl group, or a substituted or unsubstituted silyl
group, provided that one of n1 to n6 is an integer of 1 to 3, and
the one of R.sup.1 to R.sup.6 that corresponds to the one of n1 to
n6 is a substituent represented by Chemical Formula 2, ##STR00173##
wherein, in Chemical Formula 2, X is O or S, R.sup.7 or R.sup.8 are
selected from hydrogen, deuterium, a substituted or unsubstituted
C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30
aryl group and a substituted or unsubstituted C2 to C30 heteroaryl
group, * indicates a point where the substituent is linked to a
carbon atom or an atom except carbon, R.sup.1 and R.sup.2 are
independently present or are linked to each other to form a
condensed ring, R.sup.3 and R.sup.4 are independently present or
are linked to each other to form a condensed ring, R.sup.5 and
R.sup.6 are independently present or are linked to each other to
form a condensed ring, and when one of R.sup.1 to R.sup.6 is a
substituted or unsubstituted fluorenyl group, the substituted or
unsubstituted fluorenyl group is not directly bonded with the "N"
of Chemical Formula 1.
2. The compound of claim 1, wherein Chemical Formula 1 is
represented by one of Chemical Formulae 9 to 14: ##STR00174##
##STR00175## wherein, in Chemical Formulae 9 to 14, L.sup.1 to
L.sup.6 are each independently a substituted or unsubstituted C6 to
C30 arylene group, or a substituted or unsubstituted C2 to C30
heteroarylene group except a substituted or unsubstituted
fluorenylene group, n2 to n6 are each independently integers
ranging from 0 to 3, n7 is an integer of 1 to 3, R.sup.2 to R.sup.6
are each independently selected from hydrogen, deuterium, a
substituted or unsubstituted C1 to C30 alkyl group, a substituted
or unsubstituted C3 to C30 cycloalkyl group, a substituted or
unsubstituted C6 to C30 aryl group, a substituted or unsubstituted
C2 to C30 heteroaryl group, and a substituted or unsubstituted
silyl group, X is O or S, R.sup.7 to R.sup.12 are independently
selected from hydrogen, deuterium, a substituted or unsubstituted
C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30
aryl group and a substituted or unsubstituted C2 to C30 heteroaryl
group, and when one of R.sup.2 to R.sup.6 is a substituted or
unsubstituted fluorenyl group, the substituted or unsubstituted
fluorenyl group is not directly bonded with the "N" of Chemical
Formula 1.
3. The compound of claim 1, wherein Chemical Formula 1 is
represented by one of Chemical Formulae 15 and 18: ##STR00176##
wherein, in Chemical Formulae 15 and 18, L.sup.1 to L.sup.4 are
each independently a substituted or unsubstituted C6 to C30 arylene
group, or a substituted or unsubstituted C2 to C30 heteroarylene
group except a substituted or unsubstituted fluorenylene group, n1,
n2, and n4 are each independently integers ranging from 0 to 3, n7
is an integer of 1 to 3, R.sup.1, R.sup.2 and R.sup.4 are each
independently selected from hydrogen, deuterium, a substituted or
unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted
C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to
C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl
group and a substituted or unsubstituted silyl group, X is O or S,
R.sup.7 to R.sup.10 and R.sup.13 to R.sup.16 are independently
selected from hydrogen, deuterium, a substituted or unsubstituted
C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30
aryl group and a substituted or unsubstituted C2 to C30 heteroaryl
group, and when one of R.sup.1, R.sup.2 and R.sup.4 is a
substituted or unsubstituted fluorenyl group, the substituted or
unsubstituted fluorenyl group is not directly bonded with the "N"
of Chemical Formula 1.
4. The compound of claim 1, wherein Chemical Formula 1 is
represented by one of Chemical Formulae 19 to 21: ##STR00177##
wherein, in Chemical Formulae 19 to 21, L.sup.3 and L.sup.4 are
each independently a substituted or unsubstituted C6 to C30 arylene
group, or a substituted or unsubstituted C2 to C30 heteroarylene
group except a substituted or unsubstituted fluorenylene group, n4
is an integer of 0 to 3, n7 is an integer of 1 to 3, R.sup.4 is
selected from hydrogen, deuterium, a substituted or unsubstituted
C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30
cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl
group, a substituted or unsubstituted C2 to C30 heteroaryl group
and a substituted or unsubstituted silyl group, X is O or S,
R.sup.7 to R.sup.10 and R.sup.13 to R.sup.22 are independently
selected from hydrogen, deuterium, a substituted or unsubstituted
C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30
aryl group and a substituted or unsubstituted C2 to C30 heteroaryl
group, and when R.sup.4 is a substituted or unsubstituted fluorenyl
group, the substituted or unsubstituted fluorenyl group is not
directly bonded with the "N" of Chemical Formula 1.
5. The compound of claim 1, wherein Chemical Formula 1 is
represented by one of Chemical Formulae 22, 24, and 25:
##STR00178## wherein, in Chemical Formulae 22, 24, and 25, L.sup.1
to L.sup.4 are each independently a substituted or unsubstituted C6
to C30 arylene group, or a substituted or unsubstituted C2 to C30
heteroarylene group except a substituted or unsubstituted
fluorenylene group, n1, n2 and n4 are integers of 0 to 3, n7 is an
integer of 1 to 3, R.sup.1, R.sup.2 and R.sup.4 are selected from
hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl
group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a
substituted or unsubstituted C6 to C30 aryl group, a substituted or
unsubstituted C2 to C30 heteroaryl group and a substituted or
unsubstituted silyl group, X is O or S, R.sup.7 to R.sup.10,
R.sup.21 and R.sup.22 are independently selected from hydrogen,
deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a
substituted or unsubstituted C6 to C30 aryl group and a substituted
or unsubstituted C2 to C30 heteroaryl group, and when one of
R.sup.1, R.sup.2 and R.sup.4 is a substituted or unsubstituted
fluorenyl group, the substituted or unsubstituted fluorenyl group
is not directly bonded with the "N" of Chemical Formula 1.
6. The compound of claim 1, wherein Chemical Formula 1 is
represented by one of Chemical Formulae 27 and 28: ##STR00179##
wherein, in Chemical Formulae 27 and 28, L.sup.3 and L.sup.4 are
each independently a substituted or unsubstituted C6 to C30 arylene
group, or a substituted or unsubstituted C2 to C30 heteroarylene
group except a substituted or unsubstituted fluorenylene group, n4
is an integer of 0 to 3, n7 is an integer of 1 to 3, R.sup.4 is
selected from hydrogen, deuterium, a substituted or unsubstituted
C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30
cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl
group, a substituted or unsubstituted C2 to C30 heteroaryl group
and a substituted or unsubstituted silyl group, X is O or S,
R.sup.7 to R.sup.10 and R.sup.21 to R.sup.24 are independently
selected from hydrogen, deuterium, a substituted or unsubstituted
C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30
aryl group and a substituted or unsubstituted C2 to C30 heteroaryl
group, and when R.sup.4 is a substituted or unsubstituted fluorenyl
group, the substituted or unsubstituted fluorenyl group is not
directly bonded with the "N" of Chemical Formula 1.
7. The compound of claim 2, wherein L.sup.1 and L.sup.3 of Chemical
Formula 9; L.sup.1 of Chemical Formula 10; L.sup.3 of Chemical
Formula 11; L.sup.1, L.sup.3 and L.sup.5 of Chemical Formula 12;
L.sup.5 of Chemical Formula 13; and L.sup.1 and L.sup.3 of Chemical
Formula 14 are each independently a substituted or unsubstituted C6
to C30 arylene group, or a substituted or unsubstituted C2 to C30
heteroarylene group except a substituted or unsubstituted
fluorenylene group.
8. The compound of claim 3, wherein L.sup.3 of Chemical Formula 15,
L.sup.1 and L.sup.3 of Chemical Formula 18 are each independently a
substituted or unsubstituted C6 to C30 arylene group, or a
substituted or unsubstituted C2 to C30 heteroarylene group except a
substituted or unsubstituted fluorenylene group.
9. The compound of claim 4, wherein L.sup.3 of Chemical Formula 19,
L.sup.3 and L.sup.4 of Chemical Formula 20, L.sup.3 of Chemical
Formula 21 are each independently a substituted or unsubstituted C6
to C30 arylene group, or a substituted or unsubstituted C2 to C30
heteroarylene group except a substituted or unsubstituted
fluorenylene group.
10. The compound of claim 5, wherein L.sup.3 of Chemical Formula
22, L.sup.1 and L.sup.3 of Chemical Formula 24, L.sup.3 and L.sup.4
of Chemical Formula 25 are each independently a substituted or
unsubstituted C6 to C30 arylene group, or a substituted or
unsubstituted C2 to C30 heteroarylene group except a substituted or
unsubstituted fluorenylene group.
11. The compound of claim 6, wherein L.sup.3 of Chemical Formula 27
and L.sup.3 and L.sup.4 of Chemical Formula 28 are each
independently a substituted or unsubstituted C6 to C30 arylene
group, or a substituted or unsubstituted C2 to C30 heteroarylene
group except a substituted or unsubstituted fluorenylene group.
12. The compound of claim 1, wherein: at least one of n1 to n6 is
an integer of 1 to 3, and the L.sup.1 to L.sup.6 are each
independently a substituted or unsubstituted C6 to C30 arylene
group except a substituted or unsubstituted fluorenylene group.
13. The compound of claim 1, wherein the R.sup.1 to R.sup.6 are
each independently hydrogen, or a substituted or unsubstituted C6
to C30 aryl group, wherein when the aryl group is a fluorenyl
group, the fluorenyl group is not directly bonded with the "N" of
Chemical Formula 1.
14. The compound of claim 1, wherein Chemical Formula 1 is
represented by one of the following compounds ##STR00180##
##STR00181## ##STR00182## ##STR00183## ##STR00184##
##STR00185##
15. An organic light emitting element comprising an anode, a
cathode and at least one organic thin layer between the anode and
the cathode, wherein at least one layer of the organic thin layer
includes the compound of claim 1.
16. The organic light emitting element of claim 15, wherein the
organic thin layer is an electron injection layer (EIL), an
electron transport layer (ETL), a hole injection layer (HIL), a
hole transport layer (HTL), an auxiliary hole transport layer
(HTL), or emission layer.
17. The organic light emitting element of claim 15, wherein the
organic thin layer is an auxiliary hole transport layer (HTL).
18. The organic light emitting element of claim 15, wherein the
compound is used as a host in an emission layer.
19. A display device comprising the organic light emitting element
of claim 15.
Description
Korean patent Application No. 10-2013-0059800, filed on May 27,
2013, in the Korean Intellectual Property Office, and entitled:
"Compound, Organic Light Emitting Element Comprising Same, and
Display Device Comprising Organic Light Emitting Element," is
incorporated by reference herein in its entirety.
BACKGROUND OF THE INVENTION
(a) Field
A compound, an organic light emitting element including the same,
and a display device including the organic light emitting element
are disclosed.
(b) Description of the Related Art
An organic optoelectric device is a device requiring a charge
exchange between an electrode and an organic material by using
holes or electrons.
An organic optoelectric device may be classified as follows in
accordance with its driving principles. A first organic
optoelectric device is an electronic device driven as follows:
excitons are generated in an organic material layer by photons from
an external light source; the excitons are separated into electrons
and holes; and the electrons and holes are transferred to different
electrodes as a current source (voltage source).
A second organic optoelectric device is an electronic device driven
as follows: a voltage or a current is applied to at least two
electrodes to inject holes and/or electrons into an organic
material semiconductor positioned at an interface of the
electrodes, and the device is driven by the injected electrons and
holes.
Examples of the organic optoelectric device includes organic
photoelectric device, an organic light emitting element, an organic
solar cell, an organic photo conductor drum, and an organic
transistor, and the like, which requires a hole injecting or
transport material, an electron injecting or transport material, or
a light emitting material.
Particularly, an organic light emitting element (organic light
emitting diode, OLED) has recently drawn attention due to an
increasing demand for a flat panel display. In general, organic
light emission refers to conversion of electrical energy into
photo-energy.
Such an organic light emitting element converts electrical energy
into light by applying current to an organic light emitting
material. It has a structure in which a functional organic material
layer is interposed between an anode and a cathode. The organic
material layer includes a multi-layer including different
materials, for example a hole injection layer (HIL), a hole
transport layer (HTL), an emission layer, an electron transport
layer (ETL), and an electron injection layer (EIL), in order to
improve efficiency and stability of an organic light emitting
element.
In such an organic light emitting element, when a voltage is
applied between an anode and a cathode, holes from the anode and
electrons from the cathode are injected to an organic material
layer and recombined to generate excitons having high energy. The
generated excitons generate light having certain wavelengths while
shifting to a ground state.
Recently, it has become known that a phosphorescent light emitting
material can be used for a light emitting material of an organic
light emitting element in addition to the fluorescent light
emitting material. Such a phosphorescent material emits lights by
transporting the electrons from a ground state to an exited state,
non-radiance transiting of a singlet exciton to a triplet exciton
through intersystem crossing, and transiting a triplet exciton to a
ground state to emit light.
As described above, in an organic light emitting element, an
organic material layer includes a light emitting material and a
charge transport material, for example a hole injection material, a
hole transport material, an electron transport material, an
electron injection material, and the like.
The light emitting material is classified as blue, green, and red
light emitting materials according to emitted colors, and yellow
and orange light emitting materials to emit colors approaching
natural colors.
When one material is used as a light emitting material, a maximum
light emitting wavelength is shifted to a long wavelength or color
purity decreases because of interactions between molecules, or
device efficiency decreases because of a light emitting quenching
effect, and therefore, a host/dopant system is included as a light
emitting material in order to improve color purity and increase
luminous efficiency and stability through energy transfer.
In order to implement excellent performance of an organic light
emitting element, a material constituting an organic material
layer, for example a hole injection material, a hole transport
material, a light emitting material, an electron transport
material, an electron injection material, and a light emitting
material such as a host and/or a dopant, should be stable and have
good efficiency. However, development of an organic material layer
forming material for an organic light emitting element has thus far
not been satisfactory and thus there is a need for a novel
material. This material development is also required for other
organic optoelectric devices.
The low molecular organic light emitting element is manufactured as
a thin film in a vacuum deposition method and can have good
efficiency and life-span performance. A polymer organic light
emitting element is manufactured in an Inkjet or spin coating
method has an advantage of low initial cost and being
large-sized.
Both low molecular organic light emitting and polymer organic light
emitting elements have an advantage of self-light emitting, high
speed response, wide viewing angle, ultra-thin, high image quality,
durability, large driving temperature range, and the like. In
particular, they have good visibility due to self-light emitting
characteristic compared with a conventional LCD (liquid crystal
display) and have an advantage of decreasing thickness and weight
of LCD up to a third, because they do not need a backlight.
In addition, since they have a response speed of a microsecond
unit, which is 1000 time faster than LCD, they can realize a
perfect motion picture without after-image. Based on these
advantages, they have been remarkably developed to have 80 times
efficiency and more than 100 times life-span since they come out
for the first time in the later 1980s and recently, they keep being
rapidly larger such as a 40-inch organic light emitting element
panel.
They are simultaneously required to have improved luminous
efficiency and life-span in order to be larger. Therefore, a stable
and efficient organic material layer material for an organic light
emitting element needs to be developed.
SUMMARY
One embodiment provides a compound being capable of providing an
organic optoelectric device having high efficiency and long
life-span.
Another embodiment provides an organic light emitting element
including the compound and a display device including the organic
light emitting element.
In one embodiment of the present invention, a compound represented
by Chemical Formula 1 is provided.
##STR00001##
In Chemical Formula 1, L.sup.1 to L.sup.6 are each independently a
substituted or unsubstituted C6 to C30 arylene group, or a
substituted or unsubstituted C2 to C30 heteroarylene group except a
substituted or unsubstituted fluorenylene group, n1 to n6 are each
independently integers ranging from 0 to 3, R.sup.1 to R.sup.6 are
each independently hydrogen, deuterium, a substituted or
unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted
C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to
C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl
group or a substituted or unsubstituted silyl group, and at least
one of the R.sup.1 to R.sup.6 is a substituent represented by
Chemical Formula 2.
##STR00002##
In Chemical Formula 2, X is O or S, R.sup.7 or R.sup.8 are selected
from hydrogen, deuterium, a substituted or unsubstituted C1 to C30
alkyl group, a substituted or unsubstituted C6 to C30 aryl group
and a substituted or unsubstituted C2 to C30 heteroaryl group, and
* indicates a point where the substituent is linked to a carbon
atom or an atom except carbon.
In Chemical Formula 1, R.sup.1 and R.sup.2 are independently
present or are linked to each other to form a condensed ring,
R.sup.3 and R.sup.4 are independently present or are linked to each
other to form a condensed ring, R.sup.5 and R.sup.6 are
independently present or are linked to each other to form a
condensed ring, and when one of R.sup.1 to R.sup.6 is a substituted
or unsubstituted fluorenyl group, the substituted or unsubstituted
fluorenyl group is not directly bonded with the "N" of Chemical
Formula 1.
The Chemical Formula 1 may be represented by one of Chemical
Formulae 3 to 29.
##STR00003## ##STR00004## ##STR00005## ##STR00006## ##STR00007##
##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012##
group, a substituted or unsubstituted benzothiophenyl group, a
substituted or unsubstituted benzimidazolyl group, a substituted or
unsubstituted indolyl group, a substituted or unsubstituted
quinolinyl group, a substituted or unsubstituted isoquinolinyl
group, a substituted or unsubstituted quinazolinyl group, a
substituted or unsubstituted quinoxalinyl group, a substituted or
unsubstituted naphthyridinyl group, a substituted or unsubstituted
benzoxazinyl group, a substituted or unsubstituted benzthiazinyl
group, a substituted or unsubstituted acridinyl group, a
substituted or unsubstituted phenazinyl group, a substituted or
unsubstituted phenothiazinyl group, a substituted or unsubstituted
phenoxazinyl group, a substituted or unsubstituted fluorenyl group,
a substituted or unsubstituted carbazolyl group, a substituted or
unsubstituted dibenzofuranyl group, a substituted or unsubstituted
dibenzothiophenyl group, or a combination thereof, but are not
limited thereto.
In Chemical Formulae 3 to 29, L.sup.1 to L.sup.6 are each
independently a substituted or unsubstituted C6 to C30 arylene
group, or a substituted or unsubstituted C2 to C30 heteroarylene
group except a substituted or unsubstituted fluorenylene group, n1
to n6 are each independently an integer of 0 to 3, n7 is an integer
of 1 to 3, R.sup.1 to R.sup.6 are each independently selected from
hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl
group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a
substituted or unsubstituted C6 to C30 aryl group, a substituted or
unsubstituted C2 to C30 heteroaryl group, and a substituted or
unsubstituted silyl group, when one of R.sup.1 to R.sup.6 is a
substituted or unsubstituted fluorenyl group, the substituted or
unsubstituted fluorenyl group is not directly bonded with "N" of
Chemical Formula 1, X is O or S, and R.sup.7 to R.sup.24 are each
independently selected from deuterium, a substituted or
unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted
C6 to C30 aryl group and a substituted or unsubstituted C2 to C30
heteroaryl group.
L.sup.3 of Chemical Formula 3, L.sup.1 and L.sup.2 of Chemical
Formula 8, L.sup.1 and L.sup.3 of Chemical Formula 9, L.sup.2 of
Chemical Formula 10, L.sup.3 of Chemical Formula 11, L.sup.1,
L.sup.3 and L.sup.5 of chemical Formula 12, L.sup.5 of Chemical
Formula 13, L.sup.1 and L.sup.3 of Chemical Formula 14, L.sup.3 of
Chemical Formula 15, L.sup.1 and L.sup.3 of Chemical Formula 18,
L.sup.3 of Chemical Formula 19, L.sup.3 and L.sup.4 of Chemical
Formula 20, L.sup.3 of Chemical Formula 21, L.sup.3 of Chemical
Formula 22, L.sup.1 and L.sup.3 of Chemical Formula 24, L.sup.3 and
L.sup.4 of Chemical Formula 25, L.sup.3 of Chemical Formula 27 and
L.sup.3 and L.sup.4 of Chemical Formula 28 may be each
independently a substituted or unsubstituted C6 to C30 arylene
group, or a substituted or unsubstituted C2 to C30 heteroarylene
group except a substituted or unsubstituted fluorenylene group.
The L.sup.1 and L.sup.6 may be each independently a substituted or
unsubstituted C6 to C30 arylene group except a substituted or
unsubstituted fluorenylene group.
In another embodiment of the present invention, provided is an
organic light emitting element that includes an anode, a cathode
and at least one organic thin layer between the anode and the
cathode, wherein at least one layer of the organic thin layer
includes the compound according to the embodiment of the present
invention.
The organic thin layer may be an electron injection layer (EIL), an
electron transport layer (ETL), a hole injection layer (HIL), a
hole transport layer (HTL), an auxiliary hole transport layer
(HTL), or emission layer.
The organic thin layer may be a hole injection layer (HIL) or a
hole transport layer (HTL).
The organic thin layer may be an auxiliary hole transport layer
(HTL).
The organic thin layer may be an emission layer.
The compound may be used as a host in an emission layer.
In yet another embodiment of the present invention, a display
device including the organic light emitting element according to
the embodiment of the present invention is provided.
An organic optoelectric device including the compound according to
the embodiment of the present invention has excellent
electrochemical and thermal stability, improved life-span
characteristics, and high luminous efficiency at a low driving
voltage. In addition, the compound may be appropriate for a
solution process.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 and 2 are cross-sectional views showing various embodiments
of organic light emitting elements according to embodiments of the
present invention.
FIG. 3 shows an .sup.1H-NMR result of a compound A-34 according to
Example 1.
FIG. 4 shows a PL (photoluminescence) wavelength measurement result
of the compound A-34 according to Example 1.
TABLE-US-00001 <Description of Reference Numerals Indicating
Primary Elements in the Drawings> 100, 200: organic light
emitting element 110: cathode 120: anode 105: organic thin layer
130: emission layer 140: hole transport layer (HTL) 230: emission
layer + electron transport layer (ETL)
DETAILED DESCRIPTION
Hereinafter, embodiments of the present invention are described in
detail. However, these embodiments are exemplary, the present
invention is not limited thereto and the present invention is
defined by the scope of claims.
In the present specification, when a definition is not otherwise
provided, the term "substituted" refers to one substituted with a
substituent selected from deuterium, a halogen, hydroxy group, an
amino group, a substituted or unsubstituted C1 to C30 amine group,
a nitro group, a substituted or unsubstituted C1 to C40 silyl
group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C3 to C30
cycloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group, a
fluoro group, a C1 to C10 trifluoralkyl group such as a
trifluoromethyl group, or a cyano group instead of at least one
hydrogen of a substituent or a compound.
In addition, two adjacent substituents of the substituted halogen,
hydroxy group, amino group, substituted or unsubstituted C1 to C20
amine group, nitro group, substituted or unsubstituted C3 to C40
silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C3
to C30 cycloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy
group, fluoro group, C1 to C10 trifluoroalkyl group such as
trifluoromethyl group and the like, or cyano group may be fused
with each other to form a ring. Specifically, the substituted C6 to
C30 aryl group is fused with another adjacent substituted C6 to C30
aryl group to form a substituted or unsubstituted fluorene
ring.
In the present specification, when specific definition is not
otherwise provided, the term "hetero" refers to one including 1 to
3 hetero atoms selected from N, O, S, and P, and remaining carbons
in a functional group.
In the present specification, when a definition is not otherwise
provided, "alkyl group" refers to an aliphatic hydrocarbon group.
The alkyl group may be "a saturated alkyl group" without any double
bond or triple bond.
The alkyl group may be a C1 to C20 alkyl group. More specifically,
the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl
group. For example, a C1 to C4 alkyl group may have 1 to 4 carbon
atoms in an alkyl chain which may be selected from methyl, ethyl,
propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and t-butyl.
Specific examples of the alkyl group may be a methyl group, an
ethyl group, a propyl group, an isopropyl group, a butyl group, an
isobutyl group, a t-butyl group, a pentyl group, a hexyl group,
cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a
cyclohexyl group, and the like.
In the present specification, "aryl group" refers to a cyclic
substituent where all elements have p-orbitals, and these
p-orbitals forms conjugation, and includes a monocyclic or fused
ring polycyclic (i.e., rings sharing adjacent pairs of carbon
atoms) functional group.
In the present specification, "heteroaryl group" refers to aryl
group including 1 to 3 hetero atoms selected from N, O, S, and P,
and remaining carbons. When the heteroaryl group is a fused ring,
each ring may include 1 to 3 hetero atoms.
More specifically, the substituted or unsubstituted C6 to C30 aryl
group and/or the substituted or unsubstituted C2 to C30 heteroaryl
group refer to a substituted or unsubstituted phenyl group, a
substituted or unsubstituted naphthyl group, a substituted or
unsubstituted anthracenyl group, a substituted or unsubstituted
phenanthryl group, a substituted or unsubstituted naphthacenyl
group, a substituted or unsubstituted pyrenyl group, a substituted
or unsubstituted biphenylyl group, a substituted or unsubstituted
p-terphenyl group, a substituted or unsubstituted m-terphenyl
group, a substituted or unsubstituted chrysenyl group, a
substituted or unsubstituted triphenylenyl group, a substituted or
unsubstituted perylenyl group, a substituted or unsubstituted
indenyl group, a substituted or unsubstituted furanyl group, a
substituted or unsubstituted thiophenyl group, a substituted or
unsubstituted pyrrolyl group, a substituted or unsubstituted
pyrazolyl group, a substituted or unsubstituted imidazolyl group, a
substituted or unsubstituted triazolyl group, a substituted or
unsubstituted oxazolyl group, a substituted or unsubstituted
thiazolyl group, a substituted or unsubstituted oxadiazolyl group,
a substituted or unsubstituted thiadiazolyl group, a substituted or
unsubstituted pyridyl group, a substituted or unsubstituted
pyrimidinyl group, a substituted or unsubstituted pyrazinyl group,
a substituted or unsubstituted triazinyl group, a substituted or
unsubstituted benzofuranyl group, a substituted or unsubstituted
benzothiophenyl group, a substituted or unsubstituted
benzimidazolyl group, a substituted or unsubstituted indolyl group,
a substituted or unsubstituted quinolinyl group, a substituted or
unsubstituted isoquinolinyl group, a substituted or unsubstituted
quinazolinyl group, a substituted or unsubstituted quinoxalinyl
group, a substituted or unsubstituted naphthyridinyl group, a
substituted or unsubstituted benzoxazinyl group, a substituted or
unsubstituted benzthiazinyl group, a substituted or unsubstituted
acridinyl group, a substituted or unsubstituted phenazinyl group, a
substituted or unsubstituted phenothiazinyl group, a substituted or
unsubstituted phenoxazinyl group, a substituted or unsubstituted
fluorenyl group, a substituted or unsubstituted carbazolyl group, a
substituted or unsubstituted dibenzofuranyl group, a substituted or
unsubstituted dibenzothiophenyl group, or a combination thereof,
but are not limited thereto.
For more specific examples, the substituted or unsubstituted
fluorenyl group included in the substituted C6 to C30 aryl group
may be Chemical Formula 30 or 31.
##STR00013##
In Chemical Formulae 30 and 31, R.sup.25 to R.sup.28 are
independently hydrogen, deuterium, a halogen, hydroxy group, an
amino group, a substituted or unsubstituted C1 to C30 amine group,
a nitro group, a substituted or unsubstituted C1 to C40 silyl
group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, C3 to
C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy
group, a fluoro group, a C1 to C10 trifluoroalkyl group such as a
trifluoromethyl group and the like or a cyano group, and *
indicates a point where the substituent is linked to a carbon atom
or an atom except carbon.
In the present specification, hole characteristics refer to
characteristics that holes formed in the anode is easily injected
into the emission layer and transported in the emission layer due
to conductive characteristics according to HOMO level. More
specifically, it is similar to electron-repelling
characteristics.
Electron characteristics refer to characteristics that electron
formed in the cathode is easily injected into the emission layer
and transported in the emission layer due to conductive
characteristics according to LUMO level. More specifically, it is
similar to electron-withdrawing characteristics.
In one embodiment of the present invention, a compound represented
by Chemical Formula 1 is provided.
##STR00014##
In Chemical Formula 1, L.sup.1 to L.sup.6 are each independently a
substituted or unsubstituted C6 to C30 arylene group, or a
substituted or unsubstituted C2 to C30 heteroarylene group except a
substituted or unsubstituted fluorenylene group,
n1 to n6 are each independently integers ranging from 0 to 3,
R1 to R6 are each independently hydrogen, deuterium, a substituted
or unsubstituted C1 to C30 alkyl group, a substituted or
unsubstituted C3 to C30 cycloalkyl group, a substituted or
unsubstituted C6 to C30 aryl group, a substituted or unsubstituted
C2 to C30 heteroaryl group, or a substituted or unsubstituted silyl
group, and at least one of the R1 to R6 is a substituent
represented by Chemical Formula 2.
##STR00015##
In Chemical Formula 2, X is O or S, R.sup.7 or R.sup.8 are
hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl
group, a substituted or unsubstituted C6 to C30 aryl group, or a
substituted or unsubstituted C2 to C30 heteroaryl group, and *
indicates a point where the substituent is linked to a carbon atom
or an atom except carbon.
In Chemical Formula 1, R.sup.1 and R.sup.2 are independently
present or are linked to each other to form a condensed ring,
R.sup.3 and R.sup.4 are independently present or are linked to each
other to form a condensed ring, and R.sup.5 and R.sup.6 are
independently present or are linked to each other to form a
condensed ring. When one of R.sup.1 to R.sup.6 is a substituted or
unsubstituted fluorenyl group, the substituted or unsubstituted
fluorenyl group is not directly bonded with the "N" of Chemical
Formula 1.
The compound according to one embodiment of the present invention
has a substituent represented by Chemical Formula 2 at at least one
of the R.sup.1 to R.sup.6 and thus has an increased glass
transition temperature and thus, may have improved thermal
stability and in addition, has improved hole transport capability
and thus, may improve a driving voltage, efficiency and a life-span
when used to form hole injection and transport layers of an organic
light emitting element.
In addition, the compound represented by Chemical Formula 1 may
have various energy bandgaps due to various substituents.
More specifically, the Chemical Formula 1 may be represented by one
of Chemical Formulae 3 to 29.
##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020##
##STR00021## ##STR00022## ##STR00023## ##STR00024##
##STR00025##
In Chemical Formulae 3 to 29, L.sup.1 to L.sup.6 are each
independently a substituted or unsubstituted C6 to C30 arylene
group, or a substituted or unsubstituted C2 to C30 heteroarylene
group except a substituted or unsubstituted fluorenylene group, n1
to n6 are each independently an integer of 0 to 3, n7 is an integer
of 1 to 3, R.sup.1 to R.sup.6 are each independently selected from
hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl
group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a
substituted or unsubstituted C6 to C30 aryl group, a substituted or
unsubstituted C2 to C30 heteroaryl group and a substituted or
unsubstituted silyl group, and when one of R.sup.1 to R.sup.6 is a
substituted or unsubstituted fluorenyl group, the substituted or
unsubstituted fluorenyl group is not directly bonded with the "N"
of Chemical Formula 1.
X is O or S, and R.sup.7 to R.sup.24 are each independently
selected from hydrogen, deuterium, a substituted or unsubstituted
C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30
aryl group and a substituted or unsubstituted C2 to C30 heteroaryl
group.
The Chemical Formulae 3 to 29 may have an increased glass
transition temperature and may have improved thermal stability due
to at least one substituent represented by Chemical Formula 2, and
in addition, have improved hole transport capability and
resultantly, may improve efficiency and a life-span when used to
form hole injection and transport layers of an organic light
emitting element.
In addition, the compounds represented by Chemical Formulae 15 to
21 additionally include an amine compound except carbazole in
addition to the substituent represented by Chemical Formula 2 and
thus, improved hole injection characteristics since a HOMO energy
level is increased, and thus, a hole injection barrier is lowered,
and accordingly, may deteriorate a driving voltage when used to
form a hole injection layer (HIL).
In addition, the compounds represented by Chemical Formulae 22 to
29 accitionally include an amine compound and/or a carbazolyl group
in addition to the substituent represented by Chemical Formula 2
and thus, have improved thermal stability and resultantly, may
improve life-span characteristics, and in addition, have a high
triplet energy level (T1) and may have appropriate characteristics
as a host of a phosphorescent emission layer or a hole transport
material for a phosphorescent organic light emitting element.
L.sup.3 of Chemical Formula 3, L.sup.1 and L.sup.2 of Chemical
Formula 8, L.sup.1 and L.sup.3 of Chemical Formula 9, L.sup.2 of
Chemical Formula 10, L.sup.3 of Chemical Formula 11, L.sup.1
L.sup.3 and L.sup.5 of Chemical Formula 12, L.sup.5 of Chemical
Formula 13, L.sup.1 and L.sup.3 of Chemical Formula 14, L.sup.3 of
Chemical Formula 15, L.sup.1 and L.sup.3 of Chemical Formula 18,
L.sup.3 of Chemical Formula 19, L.sup.3 and L.sup.4 of Chemical
Formula 20, L.sup.3 of Chemical Formula 21, L.sup.3 of Chemical
Formula 22, L.sup.1 and L.sup.3 of Chemical Formula 24, L.sup.3 and
L.sup.4 of Chemical Formula 25, L.sup.3 of Chemical Formula 27 and
L.sup.3 and L.sup.4 of Chemical Formula 28 may be each
independently a substituted or unsubstituted C6 to C30 arylene
group, or a substituted or unsubstituted C2 to C30 heteroarylene
group except a substituted or unsubstituted fluorenylene group.
More specifically, the L.sup.1 to L.sup.6 may be each independently
a substituted or unsubstituted C6 to C30 arylene group except a
substituted or unsubstituted fluorenylene group. In this case, the
compound may have appropriate hole transport characteristics and
from a more stable thin film due to the increased molecular weight
and improved packing characteristics.
The L.sup.1 to L.sup.6 may be selectively adjusted to determine an
entire conjugation length of the compound, and a triplet energy
bandgap of the compound may be adjusted therefrom. Thereby,
characteristics of a material required of an organic optoelectric
device may be realised. In addition, the triplet energy bandgap may
also be adjusted by changing a bonding position of ortho, para, and
meta.
Specific examples of the L.sup.1 to L.sup.6 may be a substituted or
unsubstituted phenylene group, a substituted or unsubstituted
biphenylene group, a substituted or unsubstituted p-terphenylene
group, a substituted or unsubstituted m-terphenylene group, a
substituted or unsubstituted o-terphenylene group, a substituted or
unsubstituted naphthylene group, a substituted or unsubstituted
anthracenylene group, a substituted or unsubstituted phenanthrylene
group, a substituted or unsubstituted pyrenylene group, and the
like, but is not limited thereof.
The R.sup.1 to R.sup.6 may be each independently hydrogen, or a
substituted or unsubstituted C6 to C30 aryl group. In this case,
since hole and/or electron characteristics of the compound may be
appropriately adjusted, the compound may be used as an emission
layer material as well as a hole transport material by adjusting a
bandgap and a light emitting wavelength.
Specific examples of the R.sup.1 to R.sup.6 may be hydrogen, a
substituted or unsubstituted phenyl group, a substituted or
unsubstituted biphenyl group, a substituted or unsubstituted
naphthyl group, a substituted or unsubstituted anthracenyl group, a
substituted or unsubstituted phenanthrenyl group, a substituted or
unsubstituted triphenyl group, or a substituted, or unsubstituted
fluorenyl group, and when one of R.sup.1 to R.sup.6 is a
substituted or unsubstituted fluorenyl group, in Chemical Formulae
1 and Chemical Formulae 3 to 29, the substituted or unsubstituted
fluorenyl group is not directly bonded with the "N."
Specific examples of the compound according to one embodiment of
the present invention are as follows, but are not limited
thereto.
##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030##
##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035##
##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040##
##STR00041## ##STR00042## ##STR00043##
##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048##
##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053##
##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058##
##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063##
##STR00064##
##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069##
##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074##
##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079##
##STR00080## ##STR00081## ##STR00082## ##STR00083##
##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088##
##STR00089## ##STR00090## ##STR00091## ##STR00092##
In another embodiment of the present invention, provided is an
organic optoelectric device that includes an anode, cathode, and an
organic thin layer interposed between the anode and the cathode,
wherein at least one layer of the organic thin layer includes the
compound according to one embodiment of the present invention.
The compound for an organic optoelectric device is used in an
organic thin layer and thus improves life-span characteristics,
efficiency characteristic, electrochemical stability and thermal
stability of an organic optoelectric device, and lowers a driving
voltage.
The organic thin layer may be specifically a hole injection layer
(HIL), a hole transport layer (HTL), an auxiliary hole transport
layer (HTL), or an emission layer.
The organic optoelectric device may be an organic light emitting
element, an organic photoelectric device, an organic solar cell, an
organic transistor, an organic photo conductor drum, or an organic
memory device.
More specifically, the organic optoelectric device may be an
organic light emitting element. FIGS. 1 and 2 are cross-sectional
views of an organic light emitting element according to one
embodiment.
Referring to FIGS. 1 and 2, organic light emitting elements 100 and
200 according to one embodiment include an anode 120, a cathode 110
and an organic layer 105 between the anode 120 and the cathode
110.
The anode 120 includes an anode material having a large work
function to help hole injection into an organic thin layer. The
anode material includes: a metal such as nickel, platinum,
vanadium, chromium, copper, zinc, and gold, or alloys thereof; a
metal oxide such as zinc oxide, indium oxide, indium tin oxide
(ITO), and indium zinc oxide (IZO); a combination of a metal and an
oxide such as ZnO:Al and SnO.sub.2:Sb; or a conductive polymer such
as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene]
(PEDT), polypyrrole, and polyaniline, but is not limited thereto.
It is preferable to include a transparent electrode including
indium tin oxide (ITO) as an anode.
The cathode 110 includes a cathode material having a small work
function to help electron injection into an organic thin layer. The
cathode material includes: a metal such as magnesium, calcium,
sodium, potassium, titanium, indium, yttrium, lithium, gadolinium,
aluminum, silver, tin, and lead, or alloys thereof; or a
multi-layered material such as LiF/Al, Liq/Al, LiO.sub.2/Al,
LiF/Ca, LiF/Al, and BaF.sub.2/Ca, but is not limited thereto. It is
preferable to include a metal electrode including aluminum as a
cathode.
First, referring to FIG. 1, FIG. 1 shows an organic light emitting
element 100 including an emission layer 130 as an organic thin
layer 105, and the organic thin layer 105 may consist of an
emission layer 130.
Referring to FIG. 2, a double-layered organic light emitting
element 200 includes an organic thin layer 105 including an
emission layer 230 including an electron transport layer (ETL), and
a hole transport layer (HTL) 140. As shown in FIG. 2, the organic
thin layer 105 includes a double layer of the emission layer 230
and the hole transport layer (HTL) 140. The emission layer 130 also
functions as an electron transport layer (ETL), and the hole
transport layer (HTL) 140 layer has an improved binding property
with a transparent electrode such as ITO or an improved hole
transport capability. The organic thin layer 105 may further
include an electron injection layer (EIL), an electron transport
layer (ETL), an auxiliary electron transport layer (ETL), an
auxiliary hole transport layer, a hole injection layer and a
combination thereof even though they are not shown in FIG. 1 or 2.
In FIGS. 1 and 2, at least one organic thin layer 105 selected from
the emission layers 130 and 230, the hole transport layer (HTL)
140, even though being not shown, the electron injection layer
(EIL), the electron transport layer (ETL), the auxiliary electron
transport layer (ETL), the auxiliary hole transport layer (HTL),
the hole infection layer (HIL), and a combination thereof may
include the compound.
Particularly the compound may be used in the hole transport layer
(HTL) 140, the auxiliary hole transport layer (HTL), or the
emission layers 130 and 230, and when the compound is used in the
emission layers 130 and 230, it may be used as a host material in
the emission layer.
The organic light emitting element may be fabricated by: forming an
anode on a substrate; forming an organic thin layer in accordance
with a dry coating method such as evaporation, sputtering, plasma
plating, and ion plating, or a wet coating method such as spin
coating, dipping, and flow coating; and providing a cathode
thereon.
Another embodiment of the present invention provides a display
device including the organic light emitting element according to
the embodiment.
Hereinafter, the embodiments are illustrated in more detail with
reference to examples. These examples, however, are not in any
sense to be interpreted as limiting the scope of the invention.
(Preparation of Compound for Organic Optoelectric Device)
SYNTHESIS OF INTERMEDIATE
Synthesis Example 1: Synthesis of Intermediate M-1
##STR00093##
20 g (943 mmol) of 4-dibenzofuranboronic acid and 26.7 g (94.3
mmol) of 1-bromo-4-iodobenzene were put in a round-bottomed flask
and dissolved by adding 313 ml of toluene thereto, and 117 ml of an
aqueous solution obtained by dissolving 19.5 g (141.5 mmol) of
potassium carbonate was added thereto, and the mixture was
agitated. Then, 1.09 g (0.94 mmol) of
tetrakistriphenylphosphinepalladium was added thereto, and the
resulting mixture was refluxed and agitated under a nitrogen
atmosphere for 12 hours. When the reaction was complete, the
resultant was extracted with ethylacetate, the extracted solution
was dried with magnesium sulfate, filtered and concentrated under a
reduced pressure. Subsequently, a product therein was purified with
n-hexane/dichloromethane (9:1 of a volume ratio) through silica gel
column chromatography, obtaining 27 g of a target compound of a
white solid intermediate M-1 (a yield of 89%). (Calculation value:
322.00 g/mol, Measurement value: M+=322.09 g/mol, M+2=324.04
g/mol)
Synthesis Example 2: Synthesis of Intermediate M-2
##STR00094##
215 g (94.3 mmol) of 4-dibenzothiopheneboronic acid and 26.7 g
(94.3 mmol) of 1-bromo-4-iodobenzene were put in a round-bottomed
flask and dissolved by adding 313 ml of toluene thereto, and 117 ml
of an aqueous solution obtained by dissolving 19.5 g (141.5 mmol)
of potassium carbonate was added thereto, and the mixture was
agitated. Then, 1.09 g (0.94 mmol) of
tetrakistriphenylphosphinepalladium was added thereto, and the
mixture was refluxed and agitated under a nitrogen atmosphere for
12 hours. When the reaction was complete, the resultant was
extracted with ethylacetate, and the extracted solution was dried
with magnesium sulfate, filtered and concentrated under a reduced
pressure. Then, a product therefrom was purified with
n-hexane/dichloromethane (9:1 of a volume ratio) through silica gel
column chromatography, obtaining 29 g of a target compound of a
white solid intermediate M-2 (a yield of 91%). (Calculation value:
337.98 g/mol, Measurement value: M+=338.04 g/mol, M+2=340.11
g/mol)
Synthesis Example 3: Synthesis of Intermediate M-3
##STR00095##
14.7 g (94.3 mmol) of 4-chlorophenylboronic acid and 23.3 g (94.3
mmol) of 2-bromodibenzofuran were put in a round-bottomed flask and
dissolved by adding 313 ml of toluene thereto, 117 ml of an aqueous
solution obtained by dissolving 19.5 g (141.5 mmol) of potassium
carbonate was added thereto, and the mixture was agitated.
Subsequently, 1.09 g (0.94 mmol) of
tetrakistriphenylphosphinepalladium was added thereto, and the
obtained mixture was refluxed and agitated under a nitrogen
atmosphere for 12 hours.
When the reaction was complete, the resultant was extracted with
ethylacetate, the extracted solution was dried with magnesium
sulfate, filtered and concentrated under a reduced pressure.
Subsequently, a product therefrom was purified with
n-hexane/dichloromethane (9:1 of a volume ratio) through silica gel
column chromatography, obtaining 23.9 g of a target compound of a
white sold intermediate M-3 (a yield of 91%). (Calculation value:
278.05 g/mol, Measurement value: M+=278.12 g/mol, M+2=280.13
g/mol)
Synthesis Example 4: Synthesis of Intermediate M-4
##STR00096##
14.7 g (94.3 mmol) of 4-chlorophenylboronic acid and 24.8 g (94.3
mmol) of 2-bromodibenzothiophene were put in a round-bottomed flask
and dissolved by adding 313 ml of toluene thereto, 117 ml of an
aqueous solution obtained by dissolving 19.5 g (141.5 mmol) of
potassium carbonate was added thereto, and the mixture was
agitated. Then, 1.09 g (0.94 mmol) of
tetrakistriphenylphosphinepalladium was added thereto, and the
resulting mixture was refluxed and agitated under a nitrogen
atmosphere for 12 hours. When the reaction was complete, the
resultant was extracted with ethylacetate, the extracted solution
was dried with magnesium sulfate, filtered and concentrated under a
reduced pressure. Then, a product therein was purified with
n-hexane/dichloromethane (9:1 of a volume ratio) through silica gel
column chromatography, obtaining 25.6 g of a target compound of a
white solid intermediate M-4 (a yield of 92%). (Calculation value:
294.03 g/mol, Measurement value: M+=294.16 g/mol, M+2=296.13
g/mol)
Synthesis Example 5: Synthesis of Intermediate M-5
##STR00097##
10 g (30.9 mmol) of the intermediate M-1, 6.3 g (37.08 mmol) of
4-aminobiphenyl, and 5.35 g (55.6 mmol) of sodium t-butoxide were
put in a round-bottomed flask and dissolved by adding 155 ml of
toluene thereto. Then, 0.178 g (0.31 mmol) of Pd(dba).sub.2 and
0.125 g (0.62 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the resulting mixture was refluxed
and agitated under a nitrogen atmosphere for 4 hours. When the
reaction was complete, the resultant was extracted with
ethylacetate and distilled water, an organic layer obtained
therefrom was dried with magnesium sulfate, filtered and then,
concentrated under a reduced pressure. Then, a product therefrom
was purified with n-hexane/dichloromethane (7:3 volume ratio)
through silica gel column chromatography, obtaining 9.92 g of a
target compound of a white solid intermediate M-5 (a yield of 78%).
(Calculation value: 411.16 g/mol, Measurement value: M+=411.21
g/mol)
Synthesis Example 6: Synthesis of Intermediate M-6
##STR00098##
9.1 g (30.9 mmol) of the intermediate M-4 and 6.3 g (37.08 mmol) of
4-aminobiphenyl, and 5.35 g (55.6 mmol) of sodium t-butoxide were
put in a round-bottomed flask and dissolved by adding 155 ml of
toluene thereto. Then, 0.178 g (0.31 mmol) of Pd(dba).sub.2 and
0.125 g (0.62 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 4 hours. When the reaction
was complete, the resultant was extracted with ethylacetate and
distilled water, an organic layer obtained therefrom was dried with
magnesium sulfate, filtered and concentrated under a reduced
pressure. Then, a product therefrom was purified with
n-hexane/dichloromethane (7:3 of a volume ratio) through silica gel
column chromatography, obtaining 10.6 g of a target compound of a
white solid intermediate M-6 (a yield of 80%). (Calculation value:
427.14 g/mol, Measurement value: M+=427.19 g/mol)
Synthesis Example 7: Synthesis of Intermediate M-7
##STR00099##
9.1 g (30.9 mmol) of the intermediate M-4, 5.3 g (37.08 mmol) of
1-aminonaphthalene, and 5.35 g (55.6 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 155 ml
of toluene thereto. Then, 0.178 g (0.31 mmol) of Pd(dba).sub.2 and
0.125 g (0.62 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 12 hours. When the
reaction was complete, the resultant was extracted with
ethylacetate and distilled water, and an organic layer obtained
therefrom was dried with magnesium sulfate, filtered and
concentrated under a reduced pressure. Then, a product therefrom
was purified with n-hexane/dichloromethane (7:3 of a volume ratio)
through silica gel column chromatography, obtaining 10 g of a
target compound of a white solid intermediate M-7 (a yield of 81%).
(Calculation value: 401.12 g/mol, Measurement value: M+=401.15
g/mol)
Synthesis Example 8: Synthesis of Intermediate M-8
##STR00100##
31.9 g (64.7 mmol) of the intermediate M-2, 1.74 g (29.4 mmol) of
acetamide, and 17.3 g (117.6 mmol) of potassium carbonate were put
in a round-bottomed flask and dissolved by adding 130 ml of xylene
thereto. Then, 1.12 g (5.88 mmol) of copper iodide (I) and 1.04 g
(11.8 mmol) of N,N-dimethylethylenediamine were sequentially added
thereto, and the mixture was refluxed and agitated under a nitrogen
atmosphere for 48 hours. When the reaction was complete, the
resultant was extracted with toluene and distilled water, and an
organic layer obtained therefrom was dried with magnesium sulfate,
filtered and concentrated under a reduced pressure. Then, a product
therefrom was purified with n-hexane/ethylacetate (7:3 of a volume
ratio) through silica gel column chromatography, obtaining 14 g of
a target compound of an intermediate M-8 (a yield of 93%).
(Calculation value: 575.14 g/mol, Measurement value: M+=575.31
g/mol)
Synthesis Example 9: Synthesis of Intermediate M-9
##STR00101##
13 g (252 mmol) intermediate M-8 and 4.2 g (75.6 mmol) of potassium
hydroxide were put in a round-bottomed flask and dissolved by
adding 80 ml of tetrahydrofuran and 80 mL of ethanol thereto. The
mixture was refluxed and agitated under a nitrogen atmosphere for
12 hours. When the reaction was complete, the reaction solution was
concentrated under a reduced pressure, extracted with diclomethane
and distilled water, and an organic layer obtained therefrom was
dried with magnesium sulfate, filtered and concentrated under a
reduced pressure. Subsequently, a product therefrom was purified
with n-hexane/dichloromethane (7:3 of a volume ratio) through
silica gel column chromatography, obtaining 12.1 g of a target
compound of an intermediate M-9 (a yield of 90%). (Calculation
value: 533.13 g/mol, Measurement value: M+=533.26 g/mol)
Synthesis Example 10: Synthesis of Intermediate M-10
##STR00102##
25 g (92.47 mmol) of 1,3-dibromo-5-chlorobenzene, 31.3 g (184.9
mmol) of diphenylamine, and 26.7 g (277.41 mmol) of sodium
t-butoxide were put in a round-bottomed flask and dissolved by
adding 463 ml of toluene thereto. Then, 0.266 g (0.462 mmol) of
Pd(dba).sub.2 and 0.187 g (0.924 mmol) of
tri-tertiary-butylphosphine were sequentially added thereto, and
the mixture was refluxed and agitated under a nitrogen atmosphere
for 4 hours. When the reaction was complete, the resultant was
extracted with ethylacetate and distilled water, and an organic
layer obtained therefrom was dried with magnesium sulfate, filtered
and concentrated under a reduced pressure. Then, a product
therefrom was purified with n-hexane/dichloromethane (9:1 of a
volume ratio) through silica gel column chromatography, obtaining
34.7 g of a target compound of a white solid intermediate M-10 (a
yield of 84%). (Calculation value: 446.15 g/mol, Measurement value:
M+=446.23 g/mol)
Synthesis Example 11: Synthesis of Intermediate M-11
##STR00103##
25 g (92.47 mmol) of 1,3-dibromo-5-chlorobenzene, 33.9 g (184.9
mmol) of 3-methyldiphenylamine, and 26.7 g (277.41 mmol) of sodium
t-butoxide were put in a round-bottomed flask and dissolved by
adding 463 ml of toluene thereto. Then, 0266 g (0.462 mmol) of
Pd(dba).sub.2 and 0.187 g (0.924 mmol) of
tri-tertiary-butylphosphine were sequentially added thereto, and
the mixture was refluxed and agitated under a nitrogen atmosphere
for 4 hours. When the reaction was complete, the resultant was
extracted with ethylacetate and distilled water, and an organic
layer obtained therefrom was dried with magnesium sulfate, filtered
and concentrated under a reduced pressure. Then, a product
therefrom was purified with n-hexane/dichloromethane (9:1 of a
volume ratio) through silica gel column chromatography, obtaining
37.3 g of a target compound of a white solid intermediate M-11 (a
yield of 85%). (Calculation value: 474.19 g/mol, Measurement value:
M+=474.28 g/mol)
Synthesis Example 12: Synthesis of Intermediate M-12
##STR00104##
25 g (92.47 mmol) of 1,3-dibromo-5-chlorobenzene, 45.4 g (184.9
mmol) of biphenyl-4-yl-phenyl amine, and 26.7 g (277.41 mmol) of
sodium t-butoxide were put in a round-bottomed flask and dissolved
by adding 463 ml of toluene thereto. Then, 0.266 g (0.462 mmol) of
Pd(dba).sub.2 and 0.187 g (0.924 mmol) of
tri-tertiary-butylphosphine were sequentially added thereto, and
the mixture was refluxed and agitated under a nitrogen atmosphere
for 4 hours. When the reaction was complete, the resultant was
extracted with ethylacetate and distilled water, and an organic
layer obtained therefrom was dried with magnesium sulfate, filtered
and concentrated under a reduced pressure. Then, a product
therefrom was purified with n-hexane/dichloromethane (8:2 of a
volume ratio) through silica gel column chromatography, obtaining
44.9 g of a target compound of a white solid intermediate M-12 (a
yield of 81%). (Calculation value: 598.22 g/mol, Measurement value:
M+=598.37 g/mol)
Synthesis Example 13: Synthesis of Intermediate M-13
##STR00105##
25 g (92.47 mmol) of 1,3-dibromo-5-chlorobenzene, 33.9 g (184.9
mmol) of phenoxazine, and 26.7 g (277.41 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 463 ml
of toluene thereto. Then, 0.266 g (0.462 mmol) of Pd(dba).sub.2 and
0.187 g (0.924 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 4 hours. When the reaction
was complete, the resultant was extracted with ethylacetate and
distilled water, and an organic layer obtained therefrom was dried
with magnesium sulfate, filtered and concentrated under a reduced
pressure. Then, a product therefrom was purified with
n-hexane/dichloromethane (8.2 of a volume ratio) through silica gel
column chromatography, obtaining 36.9 g of a target compound of a
white solid intermediate M-13 (a yield of 84%). (Calculation value:
474.11 g/mol, Measurement value: M+=474.26 g/mol)
Synthesis Example 14: Synthesis of Intermediate M-14
##STR00106##
25 g (92.47 mmol) of 1,3-dibromo-5-chlorobenzene, 30.9 g (184.9
mmol) of carbazole, and 26.7 g (277.41 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 463 ml
of toluene thereto. Then, 0.266 g (0.462 mmol) of Pd(dba).sub.2 and
0.187 g (0.924 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 4 hours. When the reaction
was complete, the resultant was extracted with ethylacetate and
distilled water, and an organic layer obtained therefrom was dried
with magnesium sulfate, filtered and concentrated under a reduced
pressure. Then, a product therefrom was purified with
n-hexane/dichloromethane (8.2 of a volume ratio) through silica gel
column chromatography, obtaining 33.2 g of a target compound of a
white solid intermediate M-14 (a yield of 81%). (Calculation value:
442.12 g/mol, Measurement value: M+=442.36 g/mol)
Synthesis Example 15: Synthesis of Intermediate M-15
##STR00107##
25 g (92.47 mmol) of 1-bromo-3,5-dichlorobenzene, 15.5 g (92.47
mmol) of carbazole, and 13.4 g (138.7 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 463 ml
of toluene thereto. Then, 0.133 g (0.231 mmol) of Pd(dba).sub.2 and
0.094 g (0.462 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 4 hours. When the reaction
was complete, the resultant was extracted with ethylacetate and
distilled water, and an organic layer obtained therefrom was dried
with magnesium sulfate, filtered and concentrated under a reduced
pressure. Then, a product therefrom was purified with
n-hexane/dichloromethane (9:1 of a volume ratio) through silica gel
column chromatography, obtaining 24.0 g of a target compound of a
white solid intermediate M-15 (a yield of 83%). (Calculation value:
311.03 g/mol, Measurement value: M+=311.17 g/mol)
Synthesis Example 16: Synthesis of Intermediate M-16
##STR00108##
25 g (92.47 mmol) of 1-bromo-3,5-dichlorobenzene, 16.9 g (92.47
mmol) of phenoxazine, and 13.4 g (138.7 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 463 ml
of toluene thereto. Then, 0.133 g (0.231 mmol) of Pd(dba).sub.2 and
0.094 g (0.462 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 4 hours. When the reaction
was complete, the resultant was extracted with ethylacetate and
distilled water, and an organic layer obtained therefrom was dried
with magnesium sulfate, filtered and concentrated under a reduced
pressure. Then, a product therefrom was purified with
n-hexane/dichloromethane (8:2 of a volume ratio) through silica gel
column chromatography, obtaining 25.7 g of a target compound of a
white solid intermediate M-16 (a yield of 85%). (Calculation value:
327.02 g/mol, Measurement value: M+=327.27 g/mol)
Synthesis Example 17: Synthesis of Intermediate M-17
##STR00109##
10.5 g (30.9 mmol) of the intermediate M-2, 6.3 g (37.08 mmol) of
4-aminobiphenyl, and 5.35 g (55.6 mmol) of sodium t-butoxide were
put in a round-bottomed flask and dissolved in 155 ml of toluene.
Then, 0.178 g (0.31 mmol) of Pd(dba).sub.2 and 0.125 g (0.62 mmol)
of tri-tertiary-butylphosphine were sequentially added thereto, and
the mixture was refluxed and agitated under a nitrogen atmosphere
for 4 hours. When the reaction was complete, the resultant was
extracted with ethylacetate and distilled water, and an organic
layer obtained therefrom was dried with magnesium sulfate, filtered
and concentrated under a reduced pressure. Then, a product
therefrom was purified with n-hexane/dichloromethane (7:3 of a
volume ratio) through silica gel column chromatography, obtaining
9.91 g of a target compound of a white solid intermediate M-17 (a
yield of 75%).
(Calculation value: 427.14 g/mol, Measurement value: M+=427.29
g/mol)
Synthesis Example 18: Synthesis of Intermediate M-18
##STR00110##
7.6 g (30.9 mmol) of 2-bromodibenzofuran as an intermediate, 63 g
(37.08 mmol) of 4-aminobiphenyl, and 5.35 g (55.6 mmol) of sodium
t-butoxide were put in a round-bottomed flask and dissolved by
adding 155 ml of toluene. Then, 0.178 g (0.31 mmol) of
Pd(dba).sub.2 and 0.125 g (0.62 mmol) of
tri-tertiary-butylphosphine were sequentially added thereto, and
the mixture was refluxed and agitated under a nitrogen atmosphere
for 4 hours
When the reaction was complete, the resultant was extracted with
ethylacetate and distilled water, and an organic layer obtained
therefrom was dried with magnesium sulfate, filtered and
concentrated under a reduced pressure. Then, a product therefrom
was purified with n-hexane/dichloromethane (7:3 of a volume ratio)
through silica gel column chromatography, obtaining 8.1 g of a
target compound of a white solid intermediate M-18 (a yield of
78%).
(Calculation value: 335.13 g/mol, Measurement value: M+=335.42
g/mol)
Synthesis Example 19: Synthesis of Intermediate M-19
##STR00111##
8.1 g (30.9 mmol) of 2-bromodibenzothiophene as an intermediate,
5.3 g (37.08 mmol) of 2-aminonaphthalene, and 5.35 g (55.6 mmol) of
sodium t-butoxide were put in a round-bottomed flask and dissolved
by adding 155 ml of toluene thereto. Then, 0.178 g (0.31 mmol) of
Pd(dba).sub.2 and 0.125 g (0.62 mmol) of
tri-tertiary-butylphosphine were sequentially added thereto, and
the mixture was refluxed and agitated under a nitrogen atmosphere
for 4 hours. When the reaction was complete, the resultant was
extracted with ethylacetate and distilled water, and an organic
layer obtained therefrom was dried with magnesium sulfate, filtered
and concentrated under a reduced pressure. Then, a product
therefrom was purified with n-hexane/dichloromethane (7:3 of a
volume ratio) through silica gel column chromatography, obtaining
7.9 g of a target compound of a white solid intermediate M-19 (a
yield of 79%).
(Calculation value: 325.09 g/mol, Measurement value: M+=325.33
g/mol)
Synthesis Example 20: Synthesis of Intermediate M-20
##STR00112##
8.6 g (30.9 mmol) of the intermediate M-3, 5.3 g (37.08 mmol) of
I-aminonaphthalene, and 5.35 g (55.6 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 155 ml
of toluene thereto. Then, 0.178 g (0.31 mmol) of Pd(dba).sub.2 and
0.125 g (0.62 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 12 hours. When the
reaction was complete, the resultant was extracted with
ethylacetate and distilled water, and an organic layer obtained
therefrom was dried with magnesium sulfate, filtered and
concentrated under a reduced pressure. Then, a product therefrom
was purified with n-hexane/dichloromethane (7:3 of a volume ratio)
through silica gel column chromatography, obtaining 9.5 g of a
target compound of a white solid intermediate M-20 (a yield of
80%).
(Calculation value: 385.15 g/mol, Measurement value: M+=385.27
g/mol)
Synthesis Example 21: Synthesis of Intermediate M-21
##STR00113##
28.9 g (92.47 mmol) of the intermediate M-15, 16.9 g (92.47 mmol)
of phenoxazine, and 13.4 g (138.7 mmol) of sodium t-butoxide were
put in a round-bottomed flask and dissolved by adding 463 ml of
toluene thereto. Then, 0.133 g (0.231 mmol) of Pd(dba).sub.2 and
0.094 g (0.462 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 12 hours. When the
reaction was complete, the resultant was extracted with
ethylacetate and distilled water, and an organic layer obtained
therefrom was dried with magnesium sulfate, filtered and
concentrated under a reduced pressure. Then, a product therefrom
was purified with n-hexane/dichloromethane (8.2 of a volume ratio)
through silica gel column chromatography, obtaining 35.6 g of a
target compound of a white solid intermediate M-21 (a yield of
81%).
(Calculation value: 474.10 g/mol, Measurement value: M+=474.38
g/mol)
Synthesis Example 22: Synthesis of Intermediate M-22
##STR00114##
28.9 g (92.47 mmol) of the intermediate M-15, 22.7 g (92.47 mmol)
of biphenyl-4-yl-phenyl amine, and 13.4 g (138.7 mmol) of sodium
t-butoxide were put in a round-bottomed flask and dissolved by
adding 463 ml of toluene thereto. Then, 0.133 g (0.231 mmol) of
Pd(dba).sub.2 and 0.094 g (0.462 mmol) of
tri-tertiary-butylphosphine were sequentially added thereto, and
the mixture was refluxed and agitated under a nitrogen atmosphere
for 12 hours. When the reaction was complete, the resultant was
extracted with ethylacetate and distilled water, and an organic
layer obtained therefrom was dried with magnesium sulfate, filtered
and concentrated under a reduced pressure. Then, a product
therefrom was purified with n-hexane/dichloromethane (8:2 of a
volume ratio) through silica gel column chromatography, obtaining
38.1 g of a target compound of a white solid intermediate M-22 (a
yield of 79%).
(Calculation value: 520.17 g/mol, measurement value: M+=520.36
g/mol)
Synthesis of Compound for Organic Photoelectric Device
The compounds respectively represented by Chemical Formulas A-1 to
A-300, B-1 to B-20, C-1 to C-12, D-1 to D-8, E-1 to E-28 and F-1 to
F-20 were synthesized according to a method of the following
formulas 1 to 6. Specific compounds according to one embodiment of
the present invention were provided in the following [Table 1].
[General Formula 1] Synthesis of Compounds A-1 to A-291 and
A-300
##STR00115## ##STR00116##
[General Formula 2] Synthesis of Compounds B-1 to B-20
##STR00117## ##STR00118##
[General Formula 3] Synthesis of Compounds C-1 to C-12
##STR00119## ##STR00120##
[General Formula 4] Synthesis of Compounds D-1 to D-8
##STR00121##
[General Formula 5] Synthesis of Compounds E-1 to E-28
##STR00122## ##STR00123##
[General Formula 6] Synthesis of F-1 to F-20 Compounds
##STR00124##
TABLE-US-00002 TABLE 1 Final synthesis reaction Syn- intermediate
thesis halogen method compound aryl amine General Formula 1-1
##STR00125## ##STR00126## General Formula 1-2 ##STR00127##
##STR00128## General Formula 1-3 ##STR00129## ##STR00130## General
Formula 1-4 ##STR00131## ##STR00132## General Formula 2-1
##STR00133## ##STR00134## General Formula 2-2 ##STR00135##
##STR00136## General Formula 3-1 ##STR00137## ##STR00138## General
Formula 3-2 ##STR00139## ##STR00140## General Formula 4
##STR00141## ##STR00142## General Formula 5-1 ##STR00143##
##STR00144## General Formula 5-2 ##STR00145## ##STR00146## General
Formula 6 ##STR00147## ##STR00148## Measure- Syn- ment thesis Final
product value method compound structure Nos. MS[M+] General Formula
1-1 ##STR00149## A-38 989.42 General Formula 1-2 ##STR00150## A-251
1125.51 General Formula 1-3 ##STR00151## A-209 1063.49 General
Formula 1-4 ##STR00152## A-203 1037.58 General Formula 2-1
##STR00153## B-3 911.57 General Formula 2-2 ##STR00154## B-10
925.59 General Formula 3-1 ##STR00155## C-4 881.43 General Formula
3-2 ##STR00156## C-9 865.51 General Formula 4 ##STR00157## D-3
823.55 General Formula 5-1 ##STR00158## E-8 945.62 General Formula
5-2 ##STR00159## E-17 909.63 General Formula 6 ##STR00160## F-12
893.57
Example 1: Synthesis of Compound A-34
The compound A-34 was synthesized through the following Reaction
Scheme 1.
##STR00161##
10 g (22.37 mmol) of the intermediate M-10, 9.2 g (22.37 mmol) of
the intermediate M-5, and 3.2 g (33.56 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 250 ml
of toluene thereto. Then, 0.129 g (0.224 mmol) of Pd(dba).sub.2 and
0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 12 hours. When the
reaction was complete, the resultant was extracted with
ethylacetate and distilled water, and an organic layer obtained
therefrom was dried with magnesium sulfate, filtered and
concentrated under a reduced pressure. Then, a product therefrom
was purified with n-hexane/dichloromethane (82 of a volume ratio)
through silica gel column chromatography, obtaining 16.9 g of a
target compound of a white solid compound A-34 (a yield of
92%).
(Calculation value: 821.34 g/mol, Measurement value: M+=821.46
g/mol)
Example 2: Synthesis of Compound A-104
The compound A-104 was synthesized through the following Reaction
Scheme 2.
##STR00162##
13.4 g (22.37 mmol) of the intermediate M-12, 9.6 g (22.37 mmol) of
the intermediate M-6, and 3.2 g (33.56 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 250 ml
of toluene thereto. Then, 0.129 g (0.224 mmol) of Pd(dba).sub.2 and
0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 12 hours. When the
reaction was complete, the resultant was extracted with
ethylacetate and distilled water, and an organic layer obtained
therefrom was dried with magnesium sulfate, filtered and
concentrated under a reduced pressure. Then, a product therefrom
was purified with n-hexane/dichloromethane (8:2 of a volume ratio)
through silica gel column chromatography, obtaining 20.6 g of a
target compound of a white solid compound A-104 (a yield of
93%).
(Calculation value: 989.38 g/mol, Measurement value: M+=989.45
g/mol)
Example 3: Synthesis of Compound A-201
The compound A-201 was synthesized through the following Reaction
Scheme 3.
##STR00163##
10.6 g (22.37 mmol) of the intermediate M-11, 11.9 g (22.37 mmol)
of intermediate M-9, and 3.2 g (33.56 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 250 ml
of toluene thereto. Then, 0.129 g (0.224 mmol) of Pd(dba).sub.2 and
0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 12 hours. When the
reaction was complete, the resultant was extracted with
ethylacetate and distilled water, and an organic layer obtained
therefrom was dried with magnesium sulfate, filtered and
concentrated under a reduced pressure. Then, a product therefrom
was purified with n-hexane/dichloromethane (8:2 of a volume ratio)
through silica gel column chromatography, obtaining 19.8 g of a
target compound of a white solid compound A-201 (a yield of
91%).
(Calculation value: 971.34 g/mol, Measurement value: M+=971.51
g/mol)
Example 4: Synthesis of Compound A-88
The compound A-88 was synthesized through the following Reaction
Scheme 4.
##STR00164##
10 g (2237 mmol) of the intermediate M-10, 9.0 g (22.37 mmol) of
the intermediate M-7, and 3.2 g (33.56 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 250 ml
of toluene thereto. Then, 0.129 g (0.224 mmol) of Pd(dba).sub.2 and
0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 12 hours. When the
reaction was complete, the resultant was extracted with
ethylacetate and distilled water, and an organic layer obtained
therefrom was dried with magnesium sulfate, filtered and
concentrated under a reduced pressure. Then, a product therefrom
was purified with n-hexane/dichloromethane (8:2 of a volume ratio)
through silica gel column chromatography, obtaining 16.5 g of a
target compound of a white solid compound A-88 (a yield of
91%).
(Calculation value: 811.30 g/mol, Measurement value: M+=811.61
g/mol)
Example 5: Synthesis of Compound B-17
The compound B-17 was synthesized through the following Reaction
Scheme 5.
##STR00165##
7.3 g (22.37 mmol) of the intermediate M-16, 14.6 g (44.74 mmol) of
the intermediate M-19, and 6.4 g (67.11 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 250 ml
of toluene thereto. Then, 0.258 g (0.448 mmol) of Pd(dba).sub.2 and
0.182 g (0.896 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 12 hours. When the
reaction was complete, the resultant was extracted with
ethylacetate and distilled water, and an organic layer obtained
therefrom was dried with magnesium sulfate, filtered and
concentrated under a reduced pressure. Then, a product therefrom
was purified with n-hexane/dichloromethane (8:2 of a volume ratio)
through silica gel column chromatography, obtaining 19.1 g of a
target compound of a light yellow solid compound B-17 (a yield of
94%).
(Calculation value: 905.25 g/mol, Measurement value: M+=905.49
g/mol)
Example 6: Synthesis of Compound C-8
The compound C-8 was synthesized through the following Reaction
Scheme 6.
##STR00166##
10.6 g (22.37 mmol) of the intermediate M-13, 8.6 g (22.37 mmol) of
the intermediate M-20, and 3.2 g (33.56 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 250 ml
of toluene thereto. Then, 0.129 g (0.224 mmol) of Pd(dba).sub.2 and
0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 12 hours. When the
reaction was complete, the resultant was extracted with
ethylacetate and distilled water, and an organic layer obtained
therefrom was dried with magnesium sulfate, filtered and
concentrated under a reduced pressure. Then, a product therefrom
was purified with n-hexane/dichloromethane (8:2 of a volume ratio)
through silica gel column chromatography, obtaining 17 g of a
target compound of a white solid compound C-8 (a yield of 92%).
(Calculation value: 823.28 g/mol, Measurement value: M+=823.41
g/mol)
Example 7: Synthesis of Compound D-6
The compound D-6 was synthesized through the following Reaction
Scheme 7.
##STR00167##
10.6 g (22.37 mmol) of the intermediate M-21, 7.5 g (22.37 mmol) of
the intermediate M-18, and 3.2 g (33.56 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 250 ml
of toluene thereto. Then, 0.129 g (0.224 mmol) of Pd(dba).sub.2 and
0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 12 hours. When the
reaction was complete, the resultant was extracted with
ethylacetate and distilled water, and an organic layer obtained
therefrom was dried with magnesium sulfate, filtered and
concentrated under a reduced pressure. Then, a product therefrom
was purified with n-hexane/dichloromethane (8:2 of a volume ratio)
through silica gel column chromatography, obtaining 16.1 g of a
target compound of a light yellow solid compound D-6 (a yield of
93%).
(Calculation value: 773.25 g/mol, Measurement value: M+=773.51
g/mol)
Example 8: Synthesis of Compound E-25
The compound E-25 was synthesized through the following Reaction
Scheme 8.
##STR00168##
11.7 g (22.37 mmol) of the intermediate M-22, 9.2 g (22.37 mmol) of
the intermediate M-5, and 3.2 g (33.56 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 250 ml
of toluene thereto. Then, 0.129 g (0.224 mmol) of Pd(dba).sub.2 and
0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 12 hours. When the
reaction was complete, the resultant was extracted with toluene and
distilled water, and an organic layer obtained therefrom was dried
with magnesium sulfate, filtered and concentrated under a reduced
pressure. Then, a product therefrom was purified with
n-hexane/dichloromethane (8:2 of a volume ratio) through silica gel
column chromatography, obtaining 18 g of a target compound of a
white solid compound E-25 (a yield of 90%).
(Calculation value: 895.36 g/mol, Measurement value: M+=895.48
g/mol)
Example 9: Synthesis of Compound F-2
The compound F-2 was synthesized through the following Reaction
Scheme 9.
##STR00169##
9.9 g (22.37 mmol) of the intermediate M-14, 9.6 g (22.37 mmol) of
the intermediate M-17, and 3.2 g (33.56 mmol) of sodium t-butoxide
were put in a round-bottomed flask and dissolved by adding 250 ml
of toluene thereto. Then, 0.129 g (0.224 mmol) of Pd(dba).sub.2 and
0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were
sequentially added thereto, and the mixture was refluxed and
agitated under a nitrogen atmosphere for 12 hours. When the
reaction was complete, the resultant was extracted with
ethylacetate and distilled water, and an organic layer obtained
therefrom was dried with magnesium sulfate, filtered and
concentrated under a reduced pressure. Then, a product therefrom
was purified with n-hexane/dichloromethane (8:2 of a volume ratio)
through silica gel column chromatography, obtaining 17.5 g of a
target compound of a white solid compound F-2 (a yield of 94%).
(Calculation value: 833.29 g/mol, Measurement value: M+=833.42
g/mol)
(Analysis and Characteristics of Prepared Compound)
1) Measurement of Molecular Weight
The molecular weight of a compound was measured to analyze its
structure by using LC-MS.
2) 1H-NMR Result Analysis
In order to analyse the structure of the compound, the compound
according to Example 1 was dissolved in a CD2Cl2 solvent, and its
1H-NMR was measured by using a 300 MHz NMR equipment. The results
are provided in FIG. 3.
3) Fluorescence Characteristic Analysis
The compound according to Example 1 was dissolved in THF, and its
PL (photoluminescence) wavelength was measured by using HITACHI
F-4500 to analyse fluorescence characteristics. The result was
provided in FIG. 4.
(Manufacture of Organic Light Emitting Diode)
Manufacture of Green Organic Light Emitting Element
Example 10
A glass substrate coated with a 1500 .ANG.-thick ITO (Indium tin
oxide) thin film was cleaned with distilled water ultrasonic wave.
Then, the substrate was ultrasonic wave-washed with a solvent such
as isopropyl alcohol, acetone, methanol and the like solvent,
dried, then, moved to a plasma cleaner, cleaned with oxygen plasma
for 5 minutes and then, moved to a vacuum depositor. This ITO
transparent electrode as used as an anode, and a 700 .ANG.-thick
hole injection and transport layer was formed on the ITO substrate
by vacuum-depositing N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine
[NPB]. Subsequently, the compound A-34 according to Example 1 was
vacuum-deposited to form a 100 .ANG.-thick auxiliary hole transport
layer (HTL). On the auxiliary hole transport layer (HTL), 300
.ANG.-thick emission layer was formed by using
(4,4'-N,N'-dicarbazole)biphenyl [CBP] as a host and doping it with
5 wt % of tri(2-phenylpyridine)iridium (III) [Ir(ppy).sub.3] as a
dopant.
Then, A 50 .ANG.-thick hole blocking layer was formed by
vacuum-depositing biphenoxy-bis(8-hydroxyquinoline)aluminum [Balq]
on the emission layer. On the hole blocking layer, a 250
.ANG.-thick electron transport layer (ETL) was formed by
vacuum-depositing tris(8-hydroxyquinoline)aluminum [Alq.sub.3], and
on the electron transport layer (ETL), a cathode was formed by
sequentially vacuum-depositing LiF to be 10 .ANG. thick and Al to
be 100 .ANG. thick, manufacturing an organic light emitting
element.
The organic light emitting element had a five organic thin layered
structure and specifically, a structure of Al 1000 .ANG./LiF 10
.ANG./Alq.sub.3 250 .ANG./Balq 50 .ANG./EML.
[CBP:Ir(ppy).sub.3=95:5] 300 .ANG./A-34 100 .ANG./NPB 700 .ANG./ITO
1500 .ANG..
Example 11
An organic light emitting element was manufactured according to the
same method as Example 10 except for using the compound A-104
according to Example 2 instead of the compound A-34 according to
Example 1.
Example 12
An organic light emitting element was manufactured according to the
same method as Example 10 except for using the compound A-201
according to Example 3 instead of the compound A-34 according to
Example 1.
Example 13
An organic light emitting element was manufactured according to the
same method as Example 10 except for using the compound D-6
according to Example 7 instead of the compound A-34 according to
Example 1.
Example 14
An organic light emitting element was manufactured according to the
same method as Example 10 except for using the compound E-25
according to Example 8 instead of the compound A-34 according to
Example 1.
Example 15
An organic light emitting element was manufactured according to the
same method as Example 10 except for using the compound F-2
according to Example 9 instead of the compound A-34 according to
Example 1.
Comparative Example 1
An organic light emitting element was manufactured according to the
same method as Example 10 except for using
N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine [NPB] instead of the
compound A-34 according to Example 1.
Comparative Example 2
An organic light emitting element was manufactured according to the
same method as Example 10 except for using TDAB instead of the
compound A-34 according to Example 1.
Manufacture of Red Organic Light Emitting Diode
Example 16
A glass substrate coated with 1500 .ANG.-thick ITO (Indium tin
oxide) thin film was cleaned with distilled water ultrasonic wave.
After washing with distilled water, the substrate was ultrasonic
wave-cleaned with a solvent such as isopropyl alcohol, acetone,
methanol and the like, dried, moved to a plasma cleaner, cleaned
for 5 minutes by using oxygen plasma and then, moved to a vacuum
depositor. This ITO transparent electrode was used as an anode, a
600 .ANG.-thick hole injection layer (HIL) was formed by
vacuum-depositing
4,4'-bis[N-[4-{N,N-bis(3-methylphenyl)amino}-phenyl]-N-phenylamino]biphen-
yl [DNTPD] on the ITO substrate. Subsequently, a 200 .ANG.-thick
hole transport layer (HTL) was formed by vacuum-depositing
N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine [NPB]. On the hole
transport layer (HTL), a 100 .ANG.-thick auxiliary hole transport
layer (HTL) was formed by vacuum-depositing the compound A-34
according to Example 1. On the auxiliary hole transport layer
(HTL), a 300 .ANG.-thick emission layer was formed by using
(4,4'-N,N'-dicarbazole)biphenyl [CBP] as a host and doping it with
7 wt % of bis(2-phenylquinoline) (acetylacetonate)iridium(III)
[Ir(pq).sub.2acac] as a dopant.
Then, on the emission layer, a 50 .ANG.-thick hole blocking layer
was formed by vacuum-depositing
biphenoxy-bis(8-hydroxyquinoline)aluminum [Balq]. On the hole
blocking layer, a 250 .ANG.-thick electron transport layer (ETL)
was formed by vacuum-depositing tris(8-hydroxyquinoline)aluminum
[Alq.sub.3], and a cathode was formed on the electron transport
layer (ETL) by sequentially vacuum-depositing LiF to be 10 .ANG.
thick and Al to be 100 .ANG.-thick, manufacturing an organic light
emitting element.
The organic light emitting element had a six organic thin layered
structure and specifically, a structure of Al 1000 .ANG./LiF 10
.ANG./Alq.sub.3 250 .ANG./Balq 50 .ANG./EML[CBP: Ir
(pq).sub.2acac=93:7] 300 .ANG./A-34 100 .ANG./NPB 700 .ANG./DNTPD
600 .ANG./ITO 1500 .ANG..
Example 17
An organic light element was manufactured according to the same
method as Example 16 except for using the compound A-104 according
to Example 2 instead of the compound A-34 according to Example
1.
Example 18
An organic light element was manufactured according to the same
method as Example 16 except for using the compound A-88 according
to Example 4 instead of the compound A-34 according to Example
1.
Example 19
An organic light element was manufactured according to the same
method as Example 16 except for using the compound B-17 according
to Example 5 instead of the compound A-34 according to Example
1.
Example 20
An organic light element was manufactured according to the same
method as Example 16 except for using the compound C-8 according to
Example 6 instead of the compound A-34 according to Example 1.
Example 21
An organic light element was manufactured according to the same
method as Example 16 except for using the compound E-25 according
to Example 8 instead of the compound A-34 according to Example
1.
Example 22
An organic light element was manufactured according to the same
method as Example 16 except for using the compound F-2 according to
Example 9 instead of the compound A-34 according to Example 1.
Comparative Example 3
An organic light element was manufactured according to the same
method as Example 16 except for using
N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine [NPB] instead of the
compound A-34 according to Example 1.
Comparative Example 4
An organic light emitting element was manufactured according to the
same method as Example 16 except for using TDAB instead of the
compound A-34 according to Example 1.
The DNTPD, NPB, TDAB, CBP, Balq, Alq3, Ir(ppy)3, Ir(pq)2acac
respectively used for the organic light emitting elements had the
following structures.
##STR00170## ##STR00171##
(Performance Measurement of Organic Light Emitting Element)
Current density and luminance changes depending on a voltage and
luminous efficiency of each organic light emitting element
according to Examples 10 to 22 and Comparative Examples 1 to 4 were
measured. The measurements were specifically performed in the
following method, and the results were provided in the following
Tables 2 and 3.
(1) Measurement of Current Density Change Depending on Voltage
Change
The obtained organic light emitting elements were measured for
current value flowing in the unit device while increasing the
voltage from 0 V to 10 V using a current-voltage meter (Keithley
2400), the measured current value was divided by area to provide
the results.
(2) Measurement of Luminance Change Depending on Voltage Change
Luminance was measured by using a luminance meter (Minolta
Cs-1000A), while the voltage of the organic light emitting elements
was increased from 0 V to 10 V.
(3) Measurement of Luminous Efficiency
Current efficiency (cd/A) and power efficiency (lm/W) at the same
luminance (cd/m.sup.2) were calculated by using the luminance,
current density, and voltages (V) from the items (1) and (2).
(4) Life-span
Half-life life-spans of the organic light emitting elements were
measured as a time when their luminance decreased down to 1/2
relative to the initial luminance (cd/m.sup.2) after emitting the
green organic light emitting elements of Examples 10 to 15,
Comparative Example 1 and Comparative Example 2 at 3,000 nit as the
initial luminance (cd/m.sup.2) and T80 life-spans of the organic
light emitting elements were measured as a time when their
luminance decreased down to 80% relative to the initial luminance
(cd/m.sup.2) after emitting the red organic light emitting elements
of Examples 16 to 22, Comparative Example 3 and Comparative Example
4 at 1,000 nit as the initial luminance (cd-m.sup.2), and measuring
their luminance decrease depending on time with a Polanonix
life-span measurement system.
TABLE-US-00003 TABLE 2 Hole Auxiliary Half trans- hole life- port
transport Driving Luminous EL span (h) layer layer voltage
efficiency peak @3000 Devices (HTL) (HTL) (V) (cd/A) (nm) nit
Example 10 NPB A-34 7.1 37.5 516 240 Example 11 NPB A-104 6.9 39.1
516 249 Example 12 NPB A-201 7.2 38.8 516 249 Example 13 NPB D-16
7.0 35.1 516 221 Example 14 NPB E-25 7.1 39.6 516 261 Example 15
NPB F-2 7.4 40.3 516 253 Comparative NPB NPB 8.2 25.8 516 175
Example 1 Comparative NPB TDAB 8.1 24.1 516 169 Example 2
(Driving Voltage and Luminous Efficiency are Measured at 1,000
nit)
Referring to the result of [Table 2], the organic light emitting
elements according to Examples 10 to 15 using an auxiliary hole
transport layer (HTL) formed of the compound according to the
present invention showed improved luminous efficiency and life-span
compared with the green phosphorescent organic light emitting
element using no auxiliary hole transport layer (HTL) according to
Comparative Example 1. In particular, the organic light emitting
element according to an exemplary embodiment of the present
invention showed at least 36% and at most 56% increased luminous
efficiency compared with the one according to Comparative Example 1
and also, at least 31% to at most 54% increased life-span compared
with the one using conventionally-known TDAB as an auxiliary hole
transport layer (HTL) according to Comparative Example 2 and thus,
turned out to be sufficiently commercialized, considering that
life-span, of an organic light emitting element is the most
important factor for the commercialization.
TABLE-US-00004 TABLE 3 Hole Auxiliary hole Driving Luminous
T80life- transport transport layer voltage efficiency EL peak span
(h) Devices layer (HTL) (HTL) (V) (cd/A) (nm) @1000 nit Example 16
NPB A-34 8.3 18.6 600 845 Example 17 NPB A-104 8.0 18.4 600 867
Example 18 NPB A-88 8.2 17.5 600 855 Example 19 NPB B-17 7.8 18.7
600 800 Example 20 NPB C-8 8.2 17.3 600 835 Example 21 NPB E-25 8.1
18.9 600 872 Example 22 NPB F-2 8.3 18.5 600 880 Comparative NPB
NPB 8.7 15.1 600 720 Example 3 Comparative NPB TDAB 8.5 16.0 600
630 Example 4
(Driving Voltage and Luminous Efficiency are Measured at 1,000
nit)
Referring to the result of [Table 3], the organic light emitting
elements using the compound of the present invention as an
auxiliary hole transport layer (HTL) according to Examples 16 to 22
showed improved luminous efficiency and life-span compared with the
red phosphorescent organic light emitting element using no
auxiliary hole transport layer (HTL) according to Comparative
Example 3. Particularly, exemplary embodiments of the present
invention largely improved luminous efficiency by at least 14% to
at most 25% compared with Comparative Example 3 and also, increased
luminous efficiency by at least 8% to at most 18% and a life-span
by at least 27% to at most 40% compared with Comparative Example 4
using TDAB as an auxiliary hole transport layer (HTL) but decreased
a driving voltage and thus, generally improved main characteristics
of a red phosphorescent diode. Considering that life-span of a
diode is the most important factor for the commercialization, the
results of the exemplary embodiments turned out to be sufficient
for the commercialization.
While this invention has been described in connection with what is
presently considered to be practical exemplary embodiments, it is
so be understood that the invention is not limited to the disclosed
embodiments, but, on the contrary, is intended to cover various
modifications and equivalent arrangements included within the
spirit and scope of the appended claims. Therefore, the
aforementioned embodiments should be understood to be exemplary but
not limiting the present invention in any way.
* * * * *